Method for processing workpiece

ABSTRACT

According to an embodiment, a wafer (W) includes a layer (EL) to be etched, an organic film (OL), an antireflection film (AL), and a mask (MK1), and a method (MT) according to an embodiment includes a step of performing an etching process on the antireflection film (AL) by using the mask (MK1) with plasma generated in a processing container (12), in the processing container (12) of a plasma processing apparatus (10) in which the wafer (W) is accommodated, and the step includes steps ST3a to ST4 of conformally forming a protective film (SX) on the surface of the mask (MK1), and steps ST6a to ST7 of etching the antireflection film (AL) by removing the antireflection film (AL) for each atomic layer by using the mask (MK1) on which the protective film (SX) is formed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of U.S. patent application Ser. No.16/898,492 filed Jun. 11, 2020, which is a Continuation of U.S. patentapplication Ser. No. 16/089,024 filed Sep. 27, 2018, which is the U.S.National Stage of International Application No. PCT/JP2017/012407 filedMar. 27, 2017, which is based on and claims the benefit of priority fromJapanese Patent Application No. 2016-147477 filed on Jul. 27, 2016, andJapanese Patent Application No. 2016-065806 filed on Mar. 29, 2016, theentire contents of which are incorporated herein by reference.

TECHNICAL FIELD

Embodiments of the present invention relate to a method for processing aworkpiece, and more particularly to a method including generation of amask.

BACKGROUND ART

As semiconductors are miniaturized, in the next-generation lithographytechnique, extreme ultra-violet (EUV) light is used, which has awavelength of 13.5 [nm] that is one digit shorter than ArF excimer laserlight (wavelength: 193 [nm]) that is currently used for manufacturing astate-of-the-art device. Since absorption of light is increased as thewavelength becomes shorter and an aspect ratio of the resist pattern ismade large and pattern collapse tends to occur because the width of theresist pattern is made very small in the generation using EUVlithography, the film thickness of a resist for EUV lithography isreduced. Specifically, an aspect ratio of about 3 or less with respectto the resist pattern width is set to a practical level. That is, in thecase of EUV processing the resist film which is the uppermost layer ofthe stacked mask, the height of the resist film is about 30 [nm] in thegeneration with the pattern width of 10 [nm], and the height of theresist film is about 20 [nm] in the generation with the pattern width of7 [nm].

In recent semiconductor devices, a finer pattern needs to be formed, sothe influence of the fluctuation of the line pattern edge shape of theresist on device performance becomes obvious. The roughness of the linepattern edge shape is expressed using line width roughness (LWR:variation in a line width [nm]) and line edge roughness (LER: variationin a position of line edge [nm]) as indices. In a case where LER or LWRwhich is an index of variation in a mask shape increases, stabilizationof a gate leakage current and a threshold voltage is hindered, the gatelength is fluctuated, and each transistor performance in the LSI circuitvaries.

In a semiconductor integrated circuit, on the same wafer, there are adense pattern area having a large area density in which a memory, alogic portion, and the like are provided, and a sparse pattern areahaving a small area density in which a peripheral circuit portion andthe like are provided. Therefore, in an etching step for manufacturingsuch a semiconductor integrated circuit, a control technique forrealizing the accuracy of a desired pattern dimension formed bylithography is required, irrespective of the density of a pattern.Techniques related to pattern formation are disclosed in PatentLiteratures 1 and 2.

An object of a plasma etching performance enhancing method described inPatent Literature 1 is to provide a method of forming a characteristicportion without bowing in a dielectric layer on a semiconductor wafer,by etching a structure defined by an etch mask using plasma. In themethod described in Patent Literature 1, a mask is formed on adielectric layer, protective silicon-containing coating is formed on anexposed surface of the mask, and the characteristic portion is etchedthrough the mask and the protective silicon-containing coating. Further,in another method, the characteristic portion is partially etched priorto forming the protective silicon-containing coating. In this way, thetechnique described in Patent Literature 1 is to use plasma to form aprotective silicon-containing coating on the resist mask and on thesidewall of the partially etched characteristic portion.

An object of a plasma etching method described in Patent Literature 2 isto provide a plasma etching method capable of suppressing variation inprocessing dimensions, in a plasma etching method by which plasmaetching is performed using an EUV-exposed resist. The method describedin Patent Literature 2 is a plasma etching method for plasma etching ofa material to be etched, with a multilayer resist having an EUV-exposedresist, an antireflection film, an inorganic film, and an organic filmas a mask, and the method includes a first step of depositing adeposited film on a surface of the resist before etching theantireflection film, a second step of etching the deposited filmdeposited on the antireflection film and the antireflection film using amixed gas of Cl₂ gas, HBr gas and N₂ gas after the first step, a thirdstep of etching the inorganic film after the second step, and a fourthstep of etching the organic film after the third step. In this way, thetechnique of Patent Literature 2 is a technique capable of suppressingvariation in processing dimensions using an EUV resist, in which adeposited film is deposited on a surface of a resist layer using plasmabefore etching a material to be etched.

CITATION LIST Patent Literature

[Patent Literature 1] Japanese Unexamined Patent Publication No.2008-60566

[Patent Literature 2] Japanese Unexamined Patent Publication No.2014-107520

SUMMARY OF INVENTION Technical Problem

The resist for EUV lithography used for forming a highly fine pattern asdescribed above has a film thickness less than half of the filmthickness of the ArF resist in the related art due to the limit oflithography. Therefore, in a case of forming such a relatively thin andhighly fine mask pattern, in the cure step, the step of etching theantireflection film, and the step of etching the organic film,improvement of a mask selection ratio, suppression of LWR and LER, andsuppression of influence due to the density of a pattern (a differencein a pattern shape due to the density of a pattern, and the like) arerequired.

As a technique for improving a mask selection ratio in the related art,there is a technique of forming a protective film on a mask by usingdeposition gas during etching of an antireflection film. However, inthis case, LWR and LER can increase due to stress caused bypolymerization reaction of deposition during etching. Further, since theextent of adhesion of deposits during etching depends on the density ofa pattern, the extent of adhesion of deposits becomes nonuniform due tothe density of a pattern, so that the influence due to the density of apattern can increase.

In recent years, a technique for etching an antireflection film by usinga method similar to the atomic layer etching (ALE) method has beenproposed. In this technique, since the amount of ions and the amount ofradicals due to etching are separately and independently controlled, bydepositing a deposited film (radical amount) of a thin film thickness (asmall amount), the antireflection film etching can be performed byrelatively low energy. In this technique, a thin protective film isformed on the resist and the antireflection film is selectively etched,so that the selection ratio of the mask (EUV resist) can be improved.Furthermore, with this technique, since the deposited film is thinned asdescribed above, the influence due to the density of a pattern (such asa difference in pattern shape due to the density of a pattern, or thelike) can also be reduced. However, according to this technique, sinceenergy is given to a layer to be etched by collision of ions, in a casewhere the film thickness of the protective film on the mask isrelatively thin, the function of protection by the protective filmdeteriorates and the LWR and LER can be increased due to resistsputtering.

Further, in the technique described in Patent Literature 1, it ispossible to form a protective film of a silicon-containing film usingplasma of SiF₄ gas and H₂ gas. However, according to this technique,when there are sparse and dense areas in the pattern, variation in theamount of film formation may occur depending on the density of apattern.

Further, in the technique described in Patent Literature 2, it ispossible to form a protective film of an organic film using plasma ofCHF₃ gas and Cl₂ gas. However, also in this technique, since acarbon-based polymerized film is formed, particularly when there issparse and dense areas in the pattern, variation in the amount ofprotection may occur depending on the density of the pattern.

As described above, when forming a highly detailed mask, it is necessaryto realize all of improvement of mask selection ratio, suppression ofLWR and LER, and suppression of influence due to the density of apattern.

Solution to Problem

In an aspect, there is provided a method for processing a workpiece. Theworkpiece includes a layer to be etched, an organic film provided on thelayer to be etched, an antireflection film provided on the organic film,and a first mask provided on the antireflection film.

The method includes a step (referred to as step a) of conformallyforming a protective film on the surface of the first mask in aprocessing container of a plasma processing apparatus in which theworkpiece is accommodated, and a step (referred to as step b) of etchingthe antireflection film by removing the antireflection film for eachatomic layer with plasma generated in the processing container, usingthe first mask on which the protective film is formed, after executionof step a.

In this way, by executing step a, a protective film having a conformalfilm thickness, which is precisely controlled, is formed on the firstmask regardless of the density difference of the mask, resistance toetching of a mask is enhanced while the shape of the mask is maintained,and by executing step b, the mask selection ratio is enhanced, and aninfluence on the mask shape (line width roughness (LWR) and line edgeroughness (LER)) by etching is reduced.

One embodiment further includes a step (referred to as step c) ofirradiating the first mask with secondary electrons by generating plasmain the processing container and applying a negative DC voltage to theupper electrode of the parallel plate electrode provided in theprocessing container, before execution of step a. In this way, since thefirst mask is irradiated with the secondary electrons before executingstep a of forming the protective film, the first mask can be modifiedbefore the formation of the protective film, and the damage of the firstmask in the subsequent steps can be suppressed.

In one embodiment, an electrode plate of the upper electrode containssilicon, and in step c, by generating plasma in the processing containerto apply a negative DC voltage to the upper electrode, silicon isreleased from the electrode plate and the first mask is covered withsilicon oxide compound containing silicon. In this way, in step c, thefirst mask is covered with the silicon oxide compound, so that thedamage of the first mask in the subsequent steps can be furthersuppressed.

In one embodiment, in step a, a protective film is conformally formed onthe surface of the first mask, by repeating a first sequence including afirst step of supplying a first gas into the processing container, asecond step of purging the space inside the processing container afterexecution of the first step, a third step of generating plasma of asecond gas in the processing container after execution of the secondstep, and a fourth step of purging the space inside the processingcontainer after execution of the third step, and in the first step,plasma of the first gas is not generated. In this way, in step a, aprotective film is conformally formed on the silicon compound on thesurface of the first mask by the same method as the atomic layerdeposition (ALD) method, so that the protection against the mask isenhanced, and a protective film that protects the mask can be formedwith a uniform film thickness.

In one embodiment, the first gas includes an organic-containingaminosilane-based gas. In this way, since the first gas includes theorganic-containing aminosilane-based gas, in the first step, a siliconreaction precursor is formed on the first mask along the atomic layer ofthe surface of the first mask.

In one embodiment, the aminosilane-based gas of the first gas mayinclude aminosilane having one to three silicon atoms. Theaminosilane-based gas of the first gas may include aminosilane with oneto three amino groups. In this way, aminosilane containing one to threesilicon atoms can be used for aminosilane-based gas of the first gas.Further, aminosilane containing one to three amino groups can be usedfor aminosilane-based gas of the first gas.

In one embodiment, the second gas includes gas containing oxygen atomsand carbon atoms. In this way, since the second gas includes oxygenatoms, in the third step, the oxygen atom bonds with the siliconreaction precursor provided on the first mask, so that the protectivefilm of silicon oxide can be formed conformally on the first mask.Further, since the second gas includes carbon atoms, erosion by oxygenatoms against the first mask can be suppressed by the carbon atoms.

In an embodiment, in step b, the antireflection film is etched byremoving the antireflection film for each atomic layer, by repeating asecond sequence including a fifth step of generating plasma of a thirdgas in the processing container and forming a mixed layer includingradicals contained in the plasma on the atomic layer of the surface ofthe antireflection film, after execution of step a, a sixth step ofpurging the space inside the processing container, after execution ofthe fifth step, a seventh step of generating plasma of a fourth gas inthe processing container and applying a bias voltage to the plasma toremove the mixed layer, after execution of the sixth step, and an eighthstep of purging the space inside the processing container, afterexecution of the seventh step. In this way, in step b, it is possible toremove the antireflection film for each atomic layer by the same methodas the atomic layer etching (ALE) method.

In one embodiment, the third gas includes fluorocarbon-based gas andrare gas. In this way, since the third gas includes fluorocarbon-basedgas, in a fifth step, fluorine radicals and carbon radicals are suppliedto the atomic layer of the surface of the antireflection film, and amixed layer including both radicals can be formed in the atomic layer ofthe surface.

In one embodiment, the fourth gas includes rare gas. In this way, sincethe fourth gas includes rare gas, in a seventh step, the mixed layerformed in the surface of an antireflection film can be removed from thesurface, by energy received by plasma of the rare gas by a bias voltage.

In an embodiment, a step of performing an etching process on the organicfilm using a second mask, with plasma generated in the processingcontainer, after execution of step b is further included, in step b, thesecond mask is formed from the antireflection film. In this way, byexecuting steps a and b, a mask whose shape is maintained and selectionratio is improved is formed on the organic film regardless of thedensity of the mask, so that the etching of the organic film by usingthe mask of such a good shape is possible and the organic film can beetched well.

Advantageous Effects of Invention

As described above, when forming a highly detailed mask, it is possibleto realize all of improvement of mask selection ratio, suppression ofLWR and LER, and suppression of influence due to the density of apattern.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a flowchart illustrating a method of an embodiment.

FIG. 2 is a diagram illustrating an example of a plasma processingapparatus.

FIGS. 3A, 3B and 3C are cross-sectional views illustrating the state ofa workpiece before and after execution of each step shown in FIG. 1.

FIGS. 4A and 4B are cross-sectional views illustrating the state of theworkpiece after execution of each step shown in FIG. 1.

FIGS. 5A, 5B and 5C are a diagram schematically illustrating a state inwhich a protective film is formed in a sequence of forming theprotective film shown in FIG. 1.

FIGS. 6A, 6B and 6C are a diagram illustrating the principle of etchingin the method illustrated in FIG. 1.

DESCRIPTION OF EMBODIMENTS

Hereinafter, various embodiments will be described in detail withreference to the accompanying drawings. The same or equivalent parts inthe drawings are denoted by the same reference numerals.

An etching method (method MT) which can be performed by using the plasmaprocessing apparatus 10 will be described below with reference toFIG. 1. FIG. 1 is a flowchart illustrating a method of an embodiment. Amethod MT of an embodiment illustrated in FIG. 1 is a method ofprocessing a workpiece (hereinafter, it may be referred to as “wafer” insome cases). The method MT is a method of etching the wafer. In themethod MT of an embodiment, it is possible to execute a series of stepsusing a single plasma processing apparatus.

FIG. 2 is a diagram illustrating an example of a plasma processingapparatus. FIG. 2 schematically illustrates a cross-sectional structureof a plasma processing apparatus 10 that can be used in variousembodiments of a method for processing the workpiece. As illustrated inFIG. 2, the plasma processing apparatus 10 is a plasma etching apparatusprovided with electrodes of parallel flat plates, and it includes aprocessing container 12. The processing container 12 has a substantiallycylindrical shape. The processing container 12 is made of, for example,aluminum, and its inner wall surface is subjected to anodic oxidationtreatment. The processing container 12 is securely grounded.

A substantially cylindrical support portion 14 is provided on the bottomportion of the processing container 12. The support portion 14 is madeof, for example, an insulating material. The insulating materialconstituting the support portion 14 may contain oxygen like quartz. Thesupport portion 14 extends in the vertical direction from the bottomportion of the processing container 12, in the processing container 12.A placement table PD is provided in the processing container 12. Theplacement table PD is supported by the support portion 14.

The placement table PD supports a wafer W on the upper surface of theplacement table PD. The placement table PD has a lower electrode LE andan electrostatic chuck ESC. The lower electrode LE includes a firstplate 18 a and a second plate 18 b. The first plate 18 a and the secondplate 18 b are made of metal such as aluminum, for example, and have asubstantially disc shape. The second plate 18 b is provided on the firstplate 18 a and is electrically connected to the first plate 18 a.

On the second plate 18 b, an electrostatic chuck ESC is provided. Theelectrostatic chuck ESC has a structure in which an electrode which is aconductive film is disposed between a pair of insulating layers orbetween a pair of insulating sheets. A DC power supply 22 iselectrically connected to the electrode of the electrostatic chuck ESCthrough a switch 23. The electrostatic chuck ESC attracts the wafer W byan electrostatic force such as a Coulomb force generated by a DC voltagefrom the DC power supply 22. Thus, the electrostatic chuck ESC can holdthe wafer W.

On the peripheral portion of the second plate 18 b, a focus ring FR isdisposed to surround the edge of the wafer W and the electrostatic chuckESC. The focus ring FR is provided to improve etching uniformity. Thefocus ring FR is made of a material appropriately selected depending onthe material of the film to be etched, and can be made of, for example,quartz.

Inside the second plate 18 b, a coolant flow path 24 is provided. Thecoolant flow path 24 constitutes a temperature control mechanism.Coolant is supplied to the coolant flow path 24 from a chiller unit (notshown) provided outside the processing container 12 through a pipe 26 a.The coolant supplied to the coolant flow path 24 is returned to thechiller unit through the pipe 26 b. In this way, the coolant is suppliedto the coolant flow path 24 so as to circulate. By controlling thetemperature of the coolant, the temperature of the wafer W supported bythe electrostatic chuck ESC is controlled.

The plasma processing apparatus 10 is provided with a gas supply line28. The gas supply line 28 supplies heat transfer gas, for example Hegas, from the heat transfer gas supply mechanism to between the uppersurface of the electrostatic chuck ESC and the back surface of the waferW.

In the plasma processing apparatus 10, a heater HT as a heating elementis provided. For example, the heater HT is embedded in the second plate18 b. A heater power supply HP is connected to the heater HT. Bysupplying power from the heater power supply HP to the heater HT, thetemperature of the placement table PD is adjusted, and the temperatureof the wafer W placed on the placement table PD is adjusted. The heaterHT may be incorporated in the electrostatic chuck ESC.

The plasma processing apparatus 10 includes an upper electrode 30. Theupper electrode 30 is disposed to face the placement table PD, above theplacement table PD. The lower electrode LE and the upper electrode 30are provided in substantially parallel to each other to constitute theparallel plate electrodes. Between the upper electrode 30 and the lowerelectrode LE, a processing space S for performing a plasma process onthe wafer W is provided.

The upper electrode 30 is supported on the upper part of the processingcontainer 12 through an insulating shielding member 32. The insulatingshielding member 32 is made of an insulating material, and containsoxygen, such as quartz, for example. The upper electrode 30 may includean electrode plate 34 and an electrode support 36. The electrode plate34 faces the processing space S, and the electrode plate 34 is providedwith a plurality of gas discharge holes 34 a. The electrode plate 34contains silicon in an embodiment. In another embodiment, the electrodeplate 34 may contain silicon oxide.

The electrode support 36 detachably supports the electrode plate 34, andcan be made of a conductive material such as aluminum, for example. Theelectrode support 36 may have a water cooling structure. Inside theelectrode support 36, a gas diffusion chamber 36 a is provided. Aplurality of gas flow holes 36 b communicating with the gas dischargeholes 34 a extend downward from the gas diffusion chamber 36 a. A gasinlet 36 c for guiding the processing gas to the gas diffusion chamber36 a is formed in the electrode support 36, and a gas supply pipe 38 isconnected to the gas inlet 36 c.

A gas source group 40 is connected to the gas supply pipe 38, through avalve group 42 and a flow rate controller group 44. The gas source group40 has a plurality of gas sources. The plurality of gas sources are asource of an organic-containing aminosilane-based gas, a source of afluorocarbon-based gas (C_(x)F_(y) gas (x and y are integers of 1 to10)), a source of a gas having oxygen atoms and carbon atoms (forexample, carbon dioxide gas, or the like), a source of nitrogen gas, asource of hydrogen containing gas, and a source of rare gas. As thefluorocarbon-based gas, any fluorocarbon-based gas such as CF₄ gas, C₄F₆gas, and C₄F₈ gas can be used. As the aminosilane-based gas, one havinga molecular structure with a relatively small number of amino groups canbe used. For example, mono aminosilane (H₃—Si—R (R is an amino groupthat contains organic matter and may be substituted)) can be used.Further, the above-mentioned aminosilane-based gas (gas contained in afirst gas G1 to be described later) can contain aminosilane which mayhave one to three silicon atoms, or can contain aminosilane having oneto three amino groups. Aminosilane having one to three silicon atoms maybe monosilane (mono aminosilane) having one to three amino groups,disilane having one to three amino groups, or trisilane having one tothree amino groups. Furthermore, the above-mentioned aminosilane mayhave an amino group which may be substituted. Further, theabove-mentioned amino group can be substituted by any one of a methylgroup, an ethyl group, a propyl group, and a butyl group. Further, themethyl group, the ethyl group, the propyl group, and the butyl group,which are mentioned above, can be substituted by halogen. As the raregas, any rare gas such as Ar gas and He gas may be used.

The valve group 42 includes a plurality of valves, and the flow ratecontroller group 44 includes a plurality of flow rate controllers suchas a mass flow controller. Each of the plurality of gas sources of thegas source group 40 is connected to a gas supply pipe 38 through thecorresponding valve of the valve group 42 and the corresponding flowrate controller of the flow rate controller group 44. Therefore, theplasma processing apparatus 10 can supply gas from one or more gassources selected from among the plurality of gas sources of the gassource group 40 into the processing container 12 at individuallyadjusted flow rates.

In the plasma processing apparatus 10, a deposit shield 46 is detachablyprovided along the inner wall of the processing container 12. Thedeposit shield 46 is also provided on the outer periphery of the supportportion 14. The deposit shield 46 prevents etching by-products(deposits) from adhering to the processing container 12, and can be madeby coating an aluminum material with ceramics such as Y₂O₃. In additionto Y₂O₃, the deposit shield can be made of a material containing oxygensuch as quartz, for example.

An exhaust plate 48 is provided on the bottom side of the processingcontainer 12 and between the support portion 14 and the side wall of theprocessing container 12. The exhaust plate 48 can be made, for example,by covering an aluminum material with ceramics such as Y₂O₃. An exhaustport 12 e is provided under the exhaust plate 48 and in the processingcontainer 12. An exhaust device 50 is connected to the exhaust port 12 ethrough an exhaust pipe 52. The exhaust device 50 includes a vacuum pumpsuch as a turbo molecular pump, and can depressurize the space insidethe processing container 12 to a predetermined degree of vacuum. Aloading/unloading port 12 g for the wafer W is provided on a side wallof the processing container 12, and the loading/unloading port 12 g canbe opened and closed by a gate valve 54.

The plasma processing apparatus 10 further includes a firstradio-frequency power supply 62 and a second radio-frequency powersupply 64. The first radio-frequency power supply 62 is a power supplythat generates a first radio-frequency power for plasma generation, andgenerates radio-frequency power of a frequency of 27 to 100 [MHz], in anexample, 60 [MHz]. In addition, the first radio-frequency power supply62 has a pulse specification and can be controlled with a frequency of 5to 10 [kHz] and a duty ratio of 50 to 100%. The first radio-frequencypower supply 62 is connected to the upper electrode 30 through amatching unit 66. The matching unit 66 is a circuit that matches theoutput impedance of the first radio-frequency power supply 62 and theinput impedance on the load side (lower electrode LE side). In addition,the first radio-frequency power supply 62 may be connected to the lowerelectrode LE through the matching unit 66.

The second radio-frequency power supply 64 is a power supply thatgenerates second radio-frequency power for attracting ions to the waferW, that is, radio-frequency bias power, and generates a frequency withinthe range of 400 [kHz] to 40.68 [MHz], in an example, radio-frequencybias power with a frequency of 13.56 [MHz]. In addition, the secondradio-frequency power supply 64 has a pulse specification and can becontrolled with a frequency of 5 to 40 [kHz] and a duty ratio of 20 to100%. The second radio-frequency power supply 64 is connected to thelower electrode LE through the matching unit 68. The matching unit 68 isa circuit that matches the output impedance of the secondradio-frequency power supply 64 and the input impedance on the load side(lower electrode LE side).

The plasma processing apparatus 10 further includes a power supply 70.The power supply 70 is connected to the upper electrode 30. The powersupply 70 applies to the upper electrode 30, a voltage for attractingpositive ions present in the processing space S to the electrode plate34. In an example, the power supply 70 is a DC power supply thatgenerates a negative DC voltage. When such a voltage is applied from thepower supply 70 to the upper electrode 30, the positive ions present inthe processing space S collide with the electrode plate 34. Thus,secondary electrons and/or silicon is released from the electrode plate34.

In an embodiment, the plasma processing apparatus 10 may further includea control unit Cnt. The control unit Cnt is a computer including aprocessor, a storage unit, an input device, a display device, and thelike, and controls each unit of the plasma processing apparatus 10.Specifically, the control unit Cnt is connected to the valve group 42,the flow rate controller group 44, the exhaust device 50, the firstradio-frequency power supply 62, the matching unit 66, the secondradio-frequency power supply 64, the matching unit 68, the power supply70, the heater power supply HP, and the chiller unit.

The control unit Cnt operates according to a program based on the inputrecipe and sends out a control signal. It is possible to control theselection and flow rate of gas selected from the gas source group 40,the exhaust by the exhaust device 50, the supply of power from the firstradio-frequency power supply 62 and the second radio-frequency powersupply 64, the voltage application from the power supply 70, the powersupply from the heater power supply HP, the coolant flow rate andcoolant temperature from the chiller unit, according to the controlsignal from the control unit Cnt. Each step of the method MT forprocessing the workpiece in this specification can be executed byoperating each unit of the plasma processing apparatus 10 under thecontrol by the control unit Cnt.

With reference to FIG. 3A, the main configuration of a wafer W preparedin step ST1 of method MT illustrated in FIG. 1 will be explained. FIGS.3A, 3B and 3C are cross-sectional views illustrating the state of theworkpiece before and after execution of each step shown in FIG. 1.

As illustrated in FIG. 3A, the wafer W prepared in step ST1 includes asubstrate SB, a layer EL to be etched, an organic film OL, anantireflection film AL, and a mask MK1 (first mask). The layer EL to beetched is provided on the substrate SB. The layer EL to be etched is alayer made of a material which is selectively etched with respect to theorganic film OL, and an insulating film is used. The layer EL to beetched is made of, for example, silicon oxide (SiO₂). Further, the layerEL to be etched can be made of other materials such as polycrystallinesilicon.

The organic film OL is provided on the layer EL to be etched. Theorganic film OL is a layer including carbon, for example, a spin-on hardmask (SOH) layer. The antireflection film AL is a silicon-containingantireflection film and is provided on the organic film OL.

The mask MK1 is provided on the antireflection film AL. The mask MK1 isa resist mask made of a resist material, and is manufactured bypatterning a resist layer by a photolithography technique. The mask MK1is, for example, an ArF resist. The mask MK1 covers partially theantireflection film AL. The mask MK1 defines an opening OP1 partiallyexposing the antireflection film AL. The pattern of the mask MK 1 is,for example, a line and space pattern, but can have patterns of variousother shapes such as a pattern that provides a circular opening inplanar view and a pattern that provides an opening of an ellipticalshape in planar view. The mask MK1 on the antireflection film AL has aheight of a value of HG1 [nm]. Hereinafter, in a case where the ratiobetween the width (W1 [nm]) of the mask MK1 and the width (W2 [nm]) ofthe opening OP1 provided by the mask MK1 is about 1:1, the mask may besaid to be “dense” (wafer (dense)), and in a case of about 1:5, the maskmay be said to be “sparse” (wafer (sparse)).

Returning to FIG. 1, the description of the method MT will be continued.In the following description, description will be made with reference toFIGS. 3A, 3B, 3C, FIGS. 4A, 4B, and FIGS. 5A, 5B and 5C together withFIG. 1. FIGS. 3A, 3B and 3C are cross-sectional views illustrating thestate of the workpiece before and after execution of each step shown inFIG. 1. FIGS. 4A and 4B are cross-sectional views illustrating the stateof the workpiece after execution of each step of the method shown inFIG. 1. FIGS. 5A, 5B and 5C are a diagram schematically illustrating astate in which a protective film is formed in a sequence of forming theprotective film shown in FIG. 1.

In step ST1, a wafer W illustrated in FIG. 3A is prepared, and the waferW is accommodated in the processing container 12 of the plasmaprocessing apparatus 10 and placed on the electrostatic chuck ESC. Instep ST1, the wafer W shown in FIG. 3A is prepared as the wafer W shownin FIG. 2, and then step ST2 and subsequent steps are executed.

In step ST2 subsequent to step ST1, the wafer W is irradiated withsecondary electrons. Step ST2 is a step of irradiating the mask MK1 withsecondary electrons by generating plasma in the processing container 12and applying a negative DC voltage to the upper electrode 30, beforeexecuting a sequence SQ1 which conformally forms a protective film(protective film SX) of silicon oxide in the mask MK1 and step ST4.

As described above, since the mask MK1 is irradiated with secondaryelectrons before execution of a series of steps of sequence SQ1 to stepST4 forming the protective film SX, the mask MK1 can be modified beforethe formation of the protective film SX and the damage of the first maskMK1 in the subsequent steps can be suppressed.

The processing contents of step ST2 will be described in detail. First,hydrogen gas and rare gas are supplied into the processing container 12,and radio-frequency power is supplied from the first radio-frequencypower supply 62, whereby plasma is generated in the processing container12. Hydrogen gas and rare gas from the gas source selected from among aplurality of gas sources of the gas source group 40 are supplied intothe processing container 12. Accordingly, positive ions in theprocessing space S are drawn into the upper electrode 30, and thepositive ions collide with the upper electrode 30. As positive ionscollide with the upper electrode 30, secondary electrons are releasedfrom the upper electrode 30. By irradiating the wafer W with thereleased secondary electrons, the mask MK1 is modified. Further, aspositive ions collide with the electrode plate 34, silicon as aconstituent material of the electrode plate 34 is released together withthe secondary electrons. The released silicon combines with oxygenreleased from the components of the plasma processing apparatus 10exposed to the plasma. The oxygen is released from, for example, memberssuch as the support portion 14, the insulating shielding member 32, andthe deposit shield 46. The combination of silicon and oxygen produces asilicon oxide compound and the silicon oxide compound is deposited onthe wafer W to cover and protect the mask MK1. In this way, in step ST2of irradiating the mask MK1 with secondary electrons, by generatingplasma in the processing container 12 to apply a negative DC voltage tothe upper electrode 30, the mask MK1 is irradiated with secondaryelectrons and silicon is released from the electrode plate 34 to coverthe mask MK1 with silicon oxide compound containing silicon. Then, afterthe mask MK1 is irradiated with secondary electrons to cover the maskMK1 with silicon oxide compound, the space inside the processingcontainer 12 is purged, and the process proceeds to step ST2 a.

As described above, in step ST2, the mask MK1 is covered with thesilicon oxide compound, so that the damage of the mask MK1 in thesubsequent steps can be further suppressed.

In step ST2, the release of silicon may be suppressed by minimizing thebias power of the second radio-frequency power supply 64 in order tomodification by the secondary electrons and form a protective film. Itis also possible to exclude step ST2 in method MT.

Subsequent to step ST2, sequence SQ1, step ST5, sequence SQ2, step ST7(sequence SQ1 to step ST7) are sequentially executed. A series of stepsof sequence SQ1 to step ST5 is a step of conformally forming aprotective film SX of silicon oxide on the surface of mask MK1, and aseries of steps of sequence SQ2 to step ST7 is a step of preciselyetching the antireflection film AL by removing the antireflection filmAL for each atomic layer by using the mask MK1 on which the protectivefilm SX of the silicon oxide film is formed, after execution of theseries of steps of sequence SQ1 to step ST5. In this way, by executing aseries of steps of sequence SQ1 to step ST5, a protective film SX havinga conformal film thickness, which is precisely controlled, is formed onthe mask regardless of the density difference of the mask, resistance tothe etching of the mask is enhanced while maintaining the shape of mask,and by executing a series of steps of sequence SQ2 to step ST7, the maskselection ratio is enhanced, and an influence on the mask shape (linewidth roughness (LWR) and line edge roughness (LER)) by etching isreduced.

Subsequent to step ST2, sequence SQ1 (first sequence) is executed once(unit cycle) or more. Sequence SQ1 and step ST4 are a step ofconformally forming a protective film SX of silicon oxide with a uniformthickness on the wafer W by the same method as the atomic layerdeposition (ALD) method, and includes step ST3 a (first step), step ST3b (second step), step ST3 c (third step), and step ST3 d (fourth step)which are executed sequentially in sequence SQL

In step ST3 a, the first gas G1 is supplied into the processingcontainer 12. Specifically, in step ST3 a, as illustrated in FIG. 5A, afirst gas G1 containing silicon is introduced into the processingcontainer 12. The first gas G1 includes an organic-containingaminosilane-based gas. The first gas G1 of an organic-containingaminosilane-based gas is supplied from the gas source selected fromamong a plurality of gas sources of the gas source group 40 into theprocessing container 12. For the first gas G1, as aminosilane-based gas,for example, mono aminosilane (H₃—Si—R (R is an organic-containing aminogroup)) is used. In step ST3 a, plasma of the first gas G1 is notgenerated.

The molecules of the first gas G1 adhere to the surface of the wafer Was a reaction precursor (layer Ly1), as shown in FIG. 5B. The first gasG1 molecule (mono aminosilane) adheres to the surface of the wafer W bychemical adsorption based on chemical bonds, and plasma is not used. Instep ST3 a, the temperature of the wafer W is about 0 degrees Celsius ormore, and about the glass transition temperature of the materialcontained in the mask MK1 or less (for example, 200 degrees Celsius orless). It is also possible to use gases other than mono aminosilane aslong as they can adhere to the surface by chemical bonds in thetemperature range and contain silicon.

The reason why the mono aminosilane is selected for the first gas G1 isthat the mono aminosilane has a molecular structure having a relativelyhigh electronegativity and polarity, which allows chemisorption to beperformed comparatively easily. The layer Ly1 of the reaction precursorformed by the adhesion of the first gas G1 molecule to the surface ofthe wafer W is in a state close to a monomolecular layer (monolayer)because the adhesion is chemical adsorption. The smaller the amino group(R) of the mono aminosilane, the smaller the molecular structure of themolecule adsorbed on the surface of the wafer W, so that the stericeffects due to the size of the molecule is reduced. Therefore, themolecule of the first gas G1 can be uniformly adsorbed on the surface ofthe wafer W, and the layer Ly1 can be formed with a uniform filmthickness on the surface of the wafer W. The layer Ly1 can beconformally formed with a uniform film thickness on the surface of thewafer W, without depending on the pattern density of the wafer W.

As described above, since the first gas G1 includes anorganic-containing aminosilane-based gas, in step ST3 a, a siliconreaction precursor (layer Ly1) is formed on the mask MK1 along theatomic layer of the surface of the mask MK1.

In step ST3 b subsequent to step ST3 a, the space inside the processingcontainer 12 is purged. Specifically, the first gas G1 supplied in stepST3 a is exhausted. In step ST3 b, as the purge gas, an inert gas suchas nitrogen gas or rare gas (for example, Ar or the like) gas may besupplied to the processing container 12. That is, the purging in stepST3 b may be any one of gas purging to flow inert gas into theprocessing container 12, or purging by evacuating. In step ST3 b,molecules excessively attached on the wafer W can also be removed. Thus,the layer Ly1 of the reaction precursor becomes an extremely thinmonomolecular layer.

In step ST3 c subsequent to step ST3 b, as shown in FIG. 5B, plasma P1of the second gas is generated in the processing container 12. Thesecond gas includes gas containing oxygen atoms and carbon atoms, andmay include, for example, carbon dioxide gas. In step ST3 c, thetemperature of the wafer W when the plasma P1 of the second gas isgenerated is about 0 degrees Celsius or more, and about the glasstransition temperature of the material contained in the mask MK1 or less(for example, 200 degrees Celsius or less). The second gas including gascontaining oxygen atoms and carbon atoms from the gas source selectedfrom among a plurality of gas sources of the gas source group 40 issupplied into the processing container 12. Then, radio-frequency poweris supplied from the first radio-frequency power supply 62. In thiscase, bias power of the second radio-frequency power supply 64 can beapplied. It is also possible to generate plasma using only the secondradio-frequency power supply 64 without using the first radio-frequencypower supply 62. The pressure in the space inside the processingcontainer 12 is set to a preset pressure by operating the exhaust device50. In this way, the plasma P1 of the second gas is generated in theprocessing container 12.

As shown in FIG. 5B, when the plasma P1 of the second gas is generated,an active species of oxygen and an active species of carbon, forexample, an oxygen radical and a carbon radical are generated, and asshown in FIG. 5C, a layer Ly2 (corresponding to a protective film SX)which is a silicon oxide film is formed as a monomolecular layer. Sincecarbon radicals can have a function of suppressing oxygen erosion to themask MK1, a silicon oxide film can be stably formed on the surface ofthe mask MK1 as a protective film. Since the binding energy of the Si—Obond of the silicon oxide film is about 192 [kcal], and is higher thanthe binding energy (about 50 to 110 [kcal], about 70 to 110 [kcal],about 100 to 120 [kcal]) of the C—C bond, C—H bond, C—F bond,respectively, which are various bonding species of the organic filmforming the mask, the silicon oxide film can function as a protectivefilm.

As described above, since the second gas includes oxygen atoms, in stepST3 c, the oxygen atom bonds with the silicon reaction precursor (layerLy1) provided on the mask MK1, so that the layer Ly2 of a silicon oxidefilm can be formed conformally on the mask MK1. Further, since thesecond gas includes carbon atoms, erosion by oxygen atoms against themask MK1 can be suppressed by the carbon atoms. Therefore, in sequenceSQ1, as in the ALD method, by executing sequence SQ1 once (unit cycle),the layer Ly2 of the silicon oxide film can be formed conformally with athin and uniform film thickness on the surface of the wafer W,regardless of the density of the mask MK1.

In step ST3 d subsequent to step ST3 c, the space inside the processingcontainer 12 is purged. Specifically, the second gas supplied in stepST3 c is exhausted. In step ST3 d, as the purge gas, an inert gas suchas nitrogen gas or rare gas (for example, Ar or the like) may besupplied to the processing container 12. That is, the purging in stepST3 d may be any one of gas purging to flow inert gas into theprocessing container 12, or purging by evacuating.

In step ST4 subsequent to sequence SQ1, it is determined whether or notto end the execution of sequence SQ1. Specifically, in step ST4, it isdetermined whether or not the number of executions of sequence SQ1 hasreached the preset number. Determination of the number of executions ofsequence SQ1 is to determine the thickness of the film of the protectivefilm SX formed on the wafer W shown in FIG. 3B. That is, the filmthickness of the protective film SX finally formed on the wafer W can besubstantially determined by the product of the film thickness of thesilicon oxide film formed by executing sequence SQ1 once (unit cycle)and the number of executions of sequence SQL Therefore, the number ofexecutions of sequence SQ1 can be set according to the desired thicknessof the protective film SX formed on the wafer W. In this way, byrepeating sequence SQ1, the protective film SX of the silicon oxide filmis conformally formed on the surface of the mask MK1.

In a case where it is determined in step ST4 that the number ofexecutions of sequence SQ1 has not reached the preset number (step ST4:NO), the execution of sequence SQ1 is repeated again. On the other hand,in a case where it is determined in step ST4 that the number ofexecutions of sequence SQ1 has reached the preset number (step ST4:YES), the execution of sequence SQ1 is ended. Thus, as illustrated inFIG. 3B, a protective film SX which is a silicon oxide film is formed onthe surface of the wafer W. That is, by repeating sequence SQ1 by apreset number of times, a protective film SX having a preset filmthickness is conformally formed on the surface of the wafer W with auniform film thickness, regardless of the density of the mask MK1. Thethickness of the film of the protective film SX provided on the mask MK1is precisely controlled by repeating sequence SQ1.

As described above, in a series of steps of sequence SQ1 and step ST4,the protective film SX is conformally formed on the silicon compound onthe surface of the mask MK1 by the same method as the ALD method, sothat the strength of protection against the mask MK1 is improved, andthe protective film SX protecting the mask MK1 can be formed with auniform film thickness.

The protective film SX formed in the series of steps of sequence SQ1 andstep ST4 includes an area R1, an area R2 and an area R3, as shown inFIG. 3B. The area R3 is the area extending along the side surface on theside surface of the mask MK1. The area R3 extends from the surface ofthe antireflection film AL to the lower side of the area R1. The area R1extends on the upper surface of the mask MK1 and on the area R3. Thearea R2 extends between adjacent areas R3, and on the surface of theantireflection film AL. As described above, in sequence SQ1, theprotective film SX is formed as in the ALD method, so that the area R1,the area R2, and the area R3 have substantially the same film thickness,regardless of the density of the mask MK1.

In step ST5 subsequent to step ST4, the protective film SX is etched(etchback) so as to remove the area R1 and the area R2. For removal ofthe area R1 and the area R2, anisotropic etching conditions arenecessary. Therefore, in step ST5, a processing gas includingfluorocarbon-based gas from the gas source selected from among aplurality of gas sources of the gas source group 40 is supplied into theprocessing container 12. Then, radio-frequency power is supplied fromthe first radio-frequency power supply 62, radio frequency bias power issupplied from the second radio-frequency power supply 64, and thepressure of the space inside the processing container 12 is set to apreset pressure by operating the exhaust device 50. In this way, plasmaof fluorocarbon-based gas is generated. The fluorine-containing activespecies in the generated plasma preferentially etches the area R1 andthe area R2 by attraction in the vertical direction by the radiofrequency bias power. As a result, as shown in FIG. 3C, the area R1 andthe area R2 are selectively removed, and the mask MS is formed by theremaining area R3. The mask MS and the mask MK1 constitutes the mask MK2on the surface of the antireflection film AL.

Subsequent to step ST5, a series of steps of sequence SQ2 to step ST7are executed. A series of steps of sequence SQ2 to step ST7 are steps ofetching the antireflection film AL.

First, sequence SQ2 (second sequence) is executed once (unit cycle) ormore, subsequent to step ST5. Sequence SQ2 is a series of steps forprecisely etching the area of the antireflection film AL not coveredwith the mask MK2 with a high selection ratio regardless of the densityof the mask MK2 by the same method as the atomic layer etching (ALE)method, and includes step ST6 a (fifth step), step ST6 b (sixth step),step ST6 c (seventh step), and step ST6 d (eighth step) sequentiallyexecuted in sequence SQ2.

In step ST6 a, plasma of a third gas is generated in the processingcontainer 12, and a mixed layer MX including radicals contained in theplasma is formed in the atomic layer of the surface of theantireflection film AL. In step ST6 a, in a state where the wafer W isplaced on the electrostatic chuck ESC, a third gas is supplied into theprocessing container 12 to generate plasma of the third gas. The thirdgas is an etchant gas suitable for etching of the antireflection film ALincluding silicon, including fluorocarbon-based gas and rare gas, whichcan be for example, C_(x)F_(y)/Ar gas. C_(x)F_(y) can be CF₄.Specifically, the third gas including fluorocarbon-based gas and raregas from the gas source selected from among the plurality of gas sourcesof the gas source group 40 is supplied into the processing container 12.Then, radio-frequency power is supplied from the first radio-frequencypower supply 62, radio frequency bias power is supplied from the secondradio-frequency power supply 64, and the pressure of the space insidethe processing container 12 is set to a preset pressure by operating theexhaust device 50. In this way, plasma of the third gas is generated inthe processing container 12. The plasma of the third gas contains carbonradicals and fluorine radicals.

FIGS. 6A, 6B and 6C are a diagram illustrating the principle of etchingin the method (sequence SQ2) illustrated in FIG. 1. In FIGS. 6A, 6B and6C, hollow circles (white circles) indicate atoms constituting theantireflection film AL, solid circles (black circles) indicate radicals,and “+” surrounded by circles indicates the ions of atoms of rare gas(for example, ions of Ar atom) included in a fourth gas to be describedlater. As shown in FIG. 6A, in step ST6 a, carbon radicals and fluorineradicals contained in the plasma of the third gas are supplied to theatomic layer of the surface of the antireflection film AL. In this way,in step ST6 a, the mixed layer MX including atoms constituting theantireflection film AL, carbon radicals and fluorine radicals is formedin the atomic layer of the surface of the antireflection film AL (seeFIG. 6A and FIG. 3C).

As described above, since the third gas includes fluorocarbon-based gas,in step ST6 a, fluorine radicals and carbon radicals are supplied to theatomic layer of the surface of the antireflection film AL, and the mixedlayer MX including both radicals can be formed in the atomic layer ofthe surface.

In addition, in the mask MK1 of the ArF resist, Si of the mask MSincluded in the mask MK2 and the carbon radicals contained in the plasmaof the third gas function as a protective film. In addition, theadjustment of the amount of fluorine radicals can be controlled by a DCvoltage by the power supply 70.

In step ST6 b subsequent to step ST6 a, the space inside the processingcontainer 12 is purged. Specifically, the third gas supplied in step ST6a is exhausted. In step ST6 b, as the purge gas, an inert gas such asnitrogen gas or rare gas (for example, Ar gas or the like) may besupplied to the processing container 12. That is, the purging in stepST6 b may be any one of gas purging to flow inert gas into theprocessing container 12, or purging by evacuating.

In step ST6 c subsequent to step ST6 b, plasma of a fourth gas isgenerated in the processing container 12 and a bias voltage is appliedto the plasma to remove the mixed layer MX. The fourth gas includes raregas, and may include, for example, Ar gas. Specifically, a fourth gasincluding rare gas (for example, Ar gas) is supplied from the selectedgas source among the plurality of gas sources of the gas source group 40into the processing container 12, radio-frequency power is supplied fromthe first radio-frequency power supply 62, radio frequency bias power issupplied from the second radio-frequency power supply 64, and thepressure in the space inside the processing container 12 is set to apreset pressure by operating the exhaust device 50. In this way, plasmaof the fourth gas is generated in the processing container 12. The ionsof the atom of the fourth gas in the generated plasma (for example, theions of Ar atom) collide with the mixed layer MX in the surface of theantireflection film AL by attraction in the vertical direction by theradio frequency bias power, and the energy is supplied to the mixedlayer MX. As shown in FIG. 6B, in step ST6 c, energy is supplied to themixed layer MX formed in the surface of the antireflection film ALthrough the ions of the atoms of the fourth gas, and this energy removesthe mixed layer MX from the antireflection film AL.

As described above, since the fourth gas includes rare gas, in step ST6c, the mixed layer MX formed in the surface of the antireflection filmAL can be removed from the surface by energy received by plasma of therare gas by a bias voltage.

In step ST6 d subsequent to step ST6 c, the space inside the processingcontainer 12 is purged. Specifically, the fourth gas supplied in stepST6 c is exhausted. In step ST6 d, as the purge gas, an inert gas suchas nitrogen gas or rare gas (for example, Ar gas or the like) may besupplied to the processing container 12. That is, the purging in stepST6 d may be any one of gas purging to flow inert gas into theprocessing container 12, or purging by evacuating. As shown in FIG. 6C,by purging performed in step ST6 c, atoms constituting the mixed layerMX in the surface of the antireflection film AL and excessive ionscontained in the plasma of the fourth gas (for example, ions of Ar atom)can be sufficiently removed.

In step ST7 subsequent to sequence SQ2, it is determined whether or notto end the execution of sequence SQ2. Specifically, in step ST7, it isdetermined whether or not the number of executions of sequence SQ2 hasreached the preset number. To determine the number of executions ofsequence SQ2 is to determine the extent (depth) of etching forantireflection film AL. Sequence SQ2 can be repeated so as to etch theantireflection film AL to the surface of the organic film OL. That is,the execution number of sequence SQ2 can be determined such that theproduct of the thickness of the antireflection film AL etched byexecuting sequence SQ2 once (unit cycle) and the number of executions ofsequence SQ2 is the total thickness of the antireflection film ALitself. Therefore, according to the thickness of the antireflection filmAL, the number of executions of sequence SQ2 can be set.

In a case where it is determined in step ST7 that the number ofexecutions of sequence SQ2 has not reached the preset number (step ST7:NO), the execution of sequence SQ2 is repeated again. On the other hand,in a case where it is determined in step ST7 that the number ofexecutions of sequence SQ2 has reached the preset number (step ST7:YES), the execution of sequence SQ2 is ended. Thus, as shown in FIG. 4A,the antireflection film AL is etched and a mask ALM is formed. That is,by repeating sequence SQ2 by a preset number of times, theantireflection film AL is etched at the same and uniform width as thewidth of the opening OP2 provided by the mask MK2 regardless of thedensity of the mask MK2 (the density of the mask MK1), and the selectionratio is also improved.

The mask ALM and the mask MK2 provide an opening OP3. The mask MK2 (maskMK1) on the mask ALM has a height of a value of HG2 [nm]. The openingOP3 has the same width as the width of the opening OP 2 provided by maskMK2 (see FIG. 3C). The mask MK2 and the mask ALM constitute the mask MK3 for the organic film OL. The value (W3 [nm]) of the width of theopening OP3 provided by the mask MK3 including the mask MK2 and the maskALM is the same as the value of width of the opening OP2 provided by themask MK2. The width of the opening OP3 formed by etching theantireflection film AL is controlled with high accuracy by repeatingsequence SQ2.

Further, since a stable silicon oxide film with a uniform and preciselycontrolled film thickness is formed on the side of the mask MK2 on theantireflection film AL in a series of steps up to step ST5, theinfluence on the shape (LWR and LER) of the mask MK2 due to etching ofthe antireflection film AL in sequence SQ2 can be reduced. In this way,since the influence on the shape of the mask MK2 due to etching insequence SQ2 can be reduced, the influence on the width of the openingOP3 formed by etching due to etching in sequence SQ2 can also be reducedand the influence due to the density of the mask MK2 (the density of themask MK1) can be reduced.

As described above, a series of steps of sequence SQ2 to step ST7 is astep executed after executing the step of conformally forming a siliconoxide film (the area R3 (mask MS) of the protective film SX) on thesurface of the mask MK1 (after execution of step ST5), and is a step ofprecisely etching the antireflection film AL by repeating sequence SQ2by using the mask MK1 (mask MK2) on which the mask MS is formed toremove the antireflection film AL for each atomic layer. Therefore, in aseries of steps of sequence SQ2 to step ST7, the antireflection film ALcan be removed for each atomic layer by the same method as the ALEmethod.

In step ST8 subsequent to step ST7: YES, the organic film OL is etched.In step ST8, after executing sequence SQ1 to step ST7 in which theetching process is performed on the antireflection film AL (after stepST7: YES), by using the plasma generated in the processing container 12,the etching process is performed on the organic film OL by using themask MK3 (second mask). The mask MK3 is formed from the antireflectionfilm AL in the step of etching the antireflection film AL (sequence SQ1to step ST7).

The process of step ST8 will be specifically described. First, aprocessing gas including nitrogen gas and hydrogen gas is supplied intothe processing container 12 from the gas source selected from among theplurality of gas sources of the gas source group 40. As the gas, aprocessing gas including oxygen may be used. Then, radio-frequency poweris supplied from the first radio-frequency power supply 62, radiofrequency bias power is supplied from the second radio-frequency powersupply 64, and the pressure of the space inside the processing container12 is set to a predetermined pressure by operating the exhaust device50. Thus, plasma of the processing gas including nitrogen gas andhydrogen gas is generated. Hydrogen radicals, which are the activespecies of hydrogen in the generated plasma, etch the area exposed fromthe mask MK 3 of the entire area of the organic film OL. As describedabove, as shown in FIG. 4B, the organic film OL is etched, so that amask OLM having the opening OP4 with the same width as the width of theopening OP3 provided by the mask MK3 (see FIG. 4A) is formed from theorganic film OL. The mask ALM and the mask OLM constitute a mask MK4 forthe layer EL to be etched. The value of the width of the opening OP4provided by the mask MK4 is the same as the value (W4 [nm]) of the width(W3 [nm]) of the opening OP3 provided by the mask MK3. Since the widthuniformity of the opening OP3 of the mask MK3 is improved by sequenceSQ2 regardless of the density of the mask MK3 (density of the mask MK2)and the shape (LWR and LER) of the mask MK3 is also good, the widthuniformity of the opening OP4 of the mask MK4 is also improvedregardless of the density of the mask MK4 (density of the mask MK3) andthe shape (LWR and LER) of the mask MK4 is also good.

As described above, by executing a series of steps from step ST2 to ST7,a mask MK3 whose shape is maintained and selection ratio is improved isformed on the organic film OL regardless of the density of the mask, sothat the etching of the organic film OL by using the mask MK3 of such agood shape is possible and the organic film OL can be etched well.

An experiment performed using the plasma processing apparatus 10 forevaluating the method MT will be described below. Experiments areperformed on a wafer (dense) and a wafer (sparse) with the followingconfiguration. The wafer (dense) and the wafer (sparse) are examples ofthe wafer W. The wafer (dense) is formed with a mask in a dense state,and the wafer (sparse) is formed with a mask in a sparse state.

<Wafer (Dense)>

-   The ratio (W1:W2) between a value (W1 [nm]) of the mask width of the    mask MK1 and a value (W2 [nm]) of the width of the opening OP1: one    to one (1:1)-   Value (HG1 [nm]) of the mask height of the mask MK1: 40 [nm]-   Value (W2 [nm]) of the width of the opening OP1 of the mask MK1:    45.0 [nm]

<Wafer (Sparse)>

-   The ratio (W1:W2) between a value (W1 [nm]) of the mask width of the    mask MK1 and a value (W2 [nm]) of the width of the opening OP1: one    to five (1:5)-   Value (HG1 [nm]) of the mask height of the mask MK1: 40 [nm]-   Value (W2 [nm]) of width of the opening OP1 of the mask MK1: 225    [nm]

Instead of a series of processes of steps ST2 to ST8, by etching theantireflection film AL and the organic film OL by normal reactive ionetching (RIE) under the following conditions, on each of the wafer(dense) and the wafer (sparse), the following results are obtained.

<Conditions> (Etching of Antireflection Film AL)

-   Value [mTorr] of pressure in processing container 12: 15 [mTorr]-   Frequency value [MHz] of first radio-frequency power supply 62 and    value [W] of radio-frequency power: 60 [MHz], 400 [W]-   Frequency value [MHz] of second radio-frequency power supply 64 and    value [W] of bias power: 13.56 [MHz], 100 [W]-   Processing gas: CF₄ gas-   Flow rate [sccm] of processing gas: 150 [sccm]-   Processing time [s]: 30 [s]

(Etching of Organic Film OL)

-   Value [mTorr] of pressure in processing container 12: 20 [mTorr]-   Frequency value [MHz] of first radio-frequency power supply 62 and    value [W] of radio-frequency power: 60 [MHz], 1000 [W]-   Frequency value [MHz] of second radio-frequency power supply 64 and    value [W] of bias power: 13.56 [MHz], 200 [W]-   Processing gas: N₂/H₂ gas-   Flow rate [sccm] of processing gas: (N₂ gas) 200 [sccm], (H₂ gas)    200 [sccm]-   Processing time [s]: 40 [s]

In a series of processes of steps ST1 to ST8, instead of a series ofprocesses of steps ST2 to ST5, by only performing step ST1, sequence SQ2(step ST6 a to ST6 d), step ST7 and step ST8, the antireflection film ALand the organic film OL are etched on each of the wafer (dense) and thewafer (sparse), and the following results are obtained.

<Conditions> (Supply of First Gas: Step ST6 a)

-   Value [mTorr] of pressure in processing container 12 in step ST6 a:    30 [mTorr]-   Frequency value [MHz] of first radio-frequency power supply 62 and    value [W] of radio-frequency power in step ST6 a: 60 [MHz], 100 [W]-   Frequency value [MHz] of second radio-frequency power supply 64 and    value [W] of bias power in step ST6 a: 13.56 [MHz], 0 [W]-   Value [V] of DC voltage of power supply 70: −1000 [V]-   Processing gas in step ST6 a: CF₄/Ar gas-   Flow rate [sccm] of processing gas in step ST6 a: (CF₄ gas) 300    [sccm], (Ar gas) 300 [sccm]-   Processing time [s] in step ST6 a: 10 [s]

(Plasma Generation of Second Gas: Step ST6 c)

-   Value [mTorr] of pressure in processing container 12 in step ST6 c:    30 [mTorr]-   Frequency value [MHz] of first radio-frequency power supply 62 and    value [W] of radio-frequency power in step ST6 c: 60 [MHz], 100 [W]-   Frequency value [MHz] of second radio-frequency power supply 64 and    value [W] of bias power in step ST6 c: 13.56 [MHz], 30 [W]-   Processing gas in step ST6 c: Ar gas-   Flow rate [sccm] of processing gas in step ST6 c: 300 [sccm]-   Processing time [s]: 25 [s]

(Determination as to End of Sequence SQ2: Step S7)

-   Number of repetitions of sequence SQ2: 30 times

(Etching of Organic Film OL: Step ST8)

-   Value [mTorr] of pressure in processing container 12: 20 [mTorr]-   Frequency value [MHz] of first radio-frequency power supply 62 and    value [W] of radio-frequency power: 60 [MHz], 1000 [W]-   Frequency value [MHz] of second radio-frequency power supply 64 and    value [W] of bias power: 13.56 [MHz], 200 [W]-   Processing gas: N₂/H₂ gas-   Flow rate [sccm] of processing gas: (N₂ gas) 200 [sccm], (H₂ gas)    200 [sccm]-   Processing time [s]: 45 [s]

By performing a series of processes of steps ST1 to ST8 on each of thewafer (dense) and the wafer (sparse), the antireflection film AL and theorganic film OL are etched, and the following results are obtained.

<Conditions> (Secondary Electron Irradiation: Step ST2)

-   Value [mTorr] of pressure in processing container 12: 30 [mTorr]-   Frequency value [MHz] of first radio-frequency power supply 62 and    value [W] of radio-frequency power: 60 [MHz], 100 [W]-   Frequency value [MHz] of second radio-frequency power supply 64 and    value [W] of bias power: 13.56 [MHz], 0 [W]-   Value [V] of DC voltage of power supply 70: −1000 [V]-   Processing gas: H₂/Ar gas-   Flow rate [sccm] of processing gas: (H₂ gas) 60 [sccm], (Ar gas) 300    [sccm]-   Processing time [s]: 10 [s]

(Supply of First Gas: Step ST3 a)

-   Value [mTorr] of pressure in processing container 12: 500 [mTorr]-   Frequency value [MHz] of first radio-frequency power supply 62 and    value [W] of radio-frequency power: 60 [MHz], 0 [W]-   Frequency value [MHz] of second radio-frequency power supply 64 and    value [W] of bias power: 13.56 [MHz], 0 [W]-   Processing gas: organic-containing aminosilane-based gas-   Flow rate [sccm] of processing gas: 50 [sccm]-   Processing time [s]: 15 [s]

(Supply of Second Gas: Step ST3 c)

-   Value [mTorr] of pressure in processing container 12: 200 [mTorr]-   Frequency value [MHz] of first radio-frequency power supply 62 and    value [W] of radio-frequency power: 60 [MHz], 300 [W]-   Pulse frequency: 10 [kHz], 50%-   Frequency value [MHz] of second radio-frequency power supply 64 and    value [W] of bias power: 13.56 [MHz], 0 [W]-   Processing gas: CO₂ gas-   Flow rate [sccm] of processing gas: 300 [sccm]-   Processing time [s]: 5 [s]

(Determination as to End of Sequence SQ1: Step S4)

-   Number of repetitions of sequence SQ1: 20 times

(Etchback: Step ST5)

-   Value [mTorr] of pressure in processing container 12: 50 [mTorr]-   Frequency value [MHz] of first radio-frequency power supply 62 and    value [W] of radio-frequency power: 60 [MHz], 300 [W]-   Frequency value [MHz] of second radio-frequency power supply 64 and    value [W] of bias power: 13.56 [MHz], 150 [W]-   Value [V] of DC voltage of power supply 70: 0[V]-   Processing gas: CF₄ gas-   Flow rate [sccm] of processing gas: 150 [sccm]-   Processing time [s]: 4 [s]

(Plasma Generation of Third Gas: Step ST6 a)

-   Value [mTorr] of pressure in processing container 12 in step ST6 a:    30 [mTorr]-   Frequency value [MHz] of first radio-frequency power supply 62 and    value [W] of radio-frequency power in step ST6 a: 60 [MHz], 100 [W]-   Frequency value [MHz] of second radio-frequency power supply 64 and    value [W] of bias power in step ST6 a: 13.56 [MHz], 0 [W]-   Value [V] of DC voltage of power supply 70: −1000 [V]-   Processing gas in step ST6 a: CF₄/Ar gas-   Flow rate [sccm] of processing gas in step ST6 a: (CF₄ gas) 300    [sccm], (Ar gas) 300 [sccm]-   Processing time [s] in step ST6 a: 10 [s]

(Plasma Generation of Fourth Gas: Step ST6 c)

-   Value [mTorr] of pressure in processing container 12 in step ST6 c:    30 [mTorr]-   Frequency value [MHz] of first radio-frequency power supply 62 and    value [W] of radio-frequency power in step ST6 c: 60 [MHz], 100 [W]-   Frequency value [MHz] of second radio-frequency power supply 64 and    value [W] of bias power in step ST6 c: 13.56 [MHz], 0 [W]-   Value [V] of DC voltage of power supply 70: 0[V]-   Processing gas in step ST6 c: Ar gas-   Flow rate [sccm] of processing gas in step ST6 c: 300 [sccm]-   Processing time [s]: 25 [s](Determination as to end of sequence SQ2:    step S7)-   Number of repetitions of sequence SQ2: 30 times

(Etching of Organic Film OL: Step ST8)

-   Value [mTorr] of pressure in processing container 12: 20 [mTorr]-   Frequency value [MHz] of first radio-frequency power supply 62 and    value [W] of radio-frequency power: 60 [MHz], 1000 [W]-   Frequency value [MHz] of second radio-frequency power supply 64 and    value [W] of bias power: 13.56 [MHz], 200 [W]-   Processing gas: N₂/H₂ gas-   Flow rate [sccm] of processing gas: (N₂ gas) 200 [sccm], (H₂ gas)    200 [sccm]-   Processing time [s]: 45 [s]

The principle of the present invention has been illustrated anddescribed above in the preferable embodiments, but it is recognized by aperson skilled in the art that the present invention can be modified inarrangements and details without deviating from such a principle. Thepresent invention is not limited to the specific configuration disclosedin the present embodiment. Accordingly, a right to make all amendmentsand changes that come from the scope of the claim and the scope ofspirit is claimed.

REFERENCE SIGNS LIST

10 . . . PLASMA PROCESSING APPARATUS; 12 . . . PROCESSING CONTAINER; 12e . . . EXHAUST PORT; 12 g . . . LOADING/UNLOADING PORT; 14 . . .SUPPORT PORTION; 18 a . . . FIRST PLATE; 18 b . . . SECOND PLATE; 22 . .. DC POWER SUPPLY; 23 . . . SWITCH; 24 . . . COOLANT FLOW PATH; 26 a . .. PIPING; 26 b . . . PIPING; 28 . . . GAS SUPPLY LINE; 30 . . . UPPERELECTRODE; 32 . . . INSULATING SHIELDING MEMBER; 34 . . . ELECTRODEPLATE; 34 a . . . GAS DISCHARGE HOLE; 36 . . . ELECTRODE SUPPORT; 36 a .. . GAS DIFFUSION CHAMBER; 36 b . . . GAS PASSAGE HOLE; 36 c . . . GASINLET; 38 . . . GAS SUPPLY PIPE; 40 . . . GAS SOURCE GROUP; 42 . . .VALVE GROUP; 44 . . . FLOW RATE CONTROLLER GROUP; 46 . . . DEPOSITSHIELD; 48 . . . EXHAUST PLATE; 50 . . . EXHAUST DEVICE; 52 . . .EXHAUST PIPE; 54 . . . GATE VALVE; 62 . . . FIRST RADIO-FREQUENCY POWERSUPPLY; 64 . . . SECOND RADIO-FREQUENCY POWER SUPPLY; 66 . . . MATCHINGUNIT; 68 . . . MATCHING UNIT; 70 . . . POWER SUPPLY; AL . . .ANTIREFLECTION FILM; ALM . . . MASK; Cnt . . . CONTROL UNIT; EL . . .LAYER TO BE ETCHED; ESC . . . ELECTROSTATIC CHUCK; FR . . . FOCUS RING;G1 . . . FIRST GAS; HP . . . HEATER POWER SUPPLY; HT . . . HEATER; LE .. . LOWER ELECTRODE; Ly1 . . . LAYER; Ly2 . . . LAYER; MK1 . . . MASK;MK2 . . . MASK; MK3 . . . MASK; MK4 . . . MASK; MS . . . MASK; OL . . .ORGANIC FILM; OLM . . . MASK; OP1 . . . OPENING; OP2 . . . OPENING; OP3. . . OPENING; OP4 . . . OPENING; P1 . . . PLASMA; PD . . . PLACEMENTTABLE; R1 . . . AREA; R2 . . . AREA; R3 . . . AREA; S . . . PROCESSINGSPACE; SB . . . SUBSTRATE; SX . . . PROTECTIVE FILM; W . . . WAFER.

1. An etching apparatus comprising: at least one processing vesselhaving at least one gas introduction port and at least one gas outlet; asubstrate support provided in the processing vessel; a plasma generator;and a controller; wherein the controller is configured to perform:providing a substrate having a silicon-containing layer and a surfacelayer portion on the silicon-containing layer; forming a protective filmon the surface layer portion; and etching the silicon-containing layerthrough the surface layer portion; wherein the forming of the protectivefilm includes: forming a precursor layer on the surface layer portion;and converting the precursor layer to the protective film by exposingthe precursor layer to first plasma; and wherein the etching of thesilicon-containing layer comprises: modifying the silicon-containinglayer by exposing the silicon-containing layer to a second plasmadifferent from the first plasma to form a modified silicon-containinglayer; and removing the modified silicon-containing layer by exposingthe modified silicon-containing layer to a third plasma different fromthe first plasma and the second plasma.
 2. The etching apparatusaccording to claim 1, wherein the controller is configured to performthe etching of the silicon-containing layer after the forming of theprotective film on the surface layer portion.
 3. The etching apparatusaccording to claim 1, wherein the controller is configured to form theprotective film conformally in the forming of the protective film. 4.The etching apparatus according to claim 1, wherein the controller isconfigured to form the precursor layer without using plasma in theforming of the precursor layer.
 5. The etching apparatus according toclaim 1, wherein, in the converting of the precursor layer into theprotective film, the controller is configured to control temperature ofthe substrate to be 0° C. or higher and equal to or lower than aglass-transition temperature of a material included in the surface layerportion.
 6. The etching apparatus according to claim 1, wherein, in theconverting of the precursor layer into the protective film, thecontroller is configured to control temperature of the substrate to 0°C. or higher and 200° C. or lower.
 7. The etching apparatus according toclaim 1, wherein, in the forming of the protective film, the controlleris configured to execute a process including the forming of theprecursor layer and the converting of the precursor layer into theprotective film repeatedly, a plurality of times.
 8. The etchingapparatus according to claim 1, wherein the controller is configured toperform a process including: etching the protective film formed on abottom portion of the surface layer portion after the forming of theprotective film and before the etching of the silicon-containing layer.9. The etching apparatus according to claim 1, wherein, in the etchingof the silicon-containing layer, the controller is configured to executea process including the forming of the modified silicon-containing layerand the removing of the modified silicon-containing layer repeatedly, aplurality of times.
 10. The etching apparatus according to claim 1,wherein the forming of the protective film and the etching of thesilicon-containing layer are performed in one processing container. 11.The etching apparatus according to claim 4, wherein the controller isconfigured to form the precursor layer using an aminosilane-based gas inthe forming of the precursor layer.
 12. The etching apparatus accordingto claim 4, wherein the controller is configured to form the precursorlayer using an aminosilane-based gas containing aminosilane having oneto three silicon atoms in the forming of the precursor layer.
 13. Theetching apparatus according to claim 4, wherein the controller isconfigured to form the precursor layer using an aminosilane-based gascontaining aminosilane having one to three amino groups in the formingof the precursor layer.
 14. The etching apparatus according to claim 1,wherein the first plasma is plasma of gas containing oxygen atoms andcarbon atoms.
 15. The etching apparatus according to claim 1, whereinthe second plasma is plasma of gas containing fluorocarbon-based gas andrare gas.
 16. The etching apparatus according to claim 1, wherein thethird plasma is plasma of gas containing rare gas.
 17. The etchingapparatus according to claim 1, wherein the silicon-containing layercontains silicon-oxide bonds.
 18. An etching method comprising:providing a substrate having a silicon-containing layer and a surfacelayer portion on the silicon-containing layer; forming a protective filmon the surface layer portion; and etching the silicon-containing layerthrough the surface layer portion; wherein the forming of the protectivefilm includes: forming a precursor layer on the surface layer portion;and converting the precursor layer to the protective film by exposingthe precursor layer to first plasma; and wherein the etching of thesilicon-containing layer comprises: modifying the silicon-containinglayer by exposing the silicon-containing layer to a second plasmadifferent from the first plasma to form a modified silicon-containinglayer; and removing the modified silicon-containing layer by exposingthe modified silicon-containing layer to a third plasma different fromthe first plasma and the second plasma.